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48
Chapter 3.
第 3 章 本章については，5 年以内に特許申請するため，非公開.
Chapter 6
50
Chapter 6
Chapter 4.
第 4 章 本章については，5 年以内に特許申請するため，非公開.
51
Chapter 6
52
Chapter 6
Chapter 5.
第 5 章 本章については，5 年以内に特許申請するため，非公開.
53
Chapter 6
54
Chapter 6
Chapter 6.
Conclusion and Perspectives
55
Chapter 6
56
Chapter 6
In the present study, I have demonstrated the application of supramolecular
chemistry to the development of sample preparation methods in electron microscopy. I
have prepared amorphous nano/microspheres and ultrathin films through self-assembly
of organofullerene molecules modified their chemical properties by the introduction of
various substituents. Since these materials are robust under atmospheric pressure and
even under high vacuum, they were useful as supporting materials of EM research to
modify the specimen location by the morphology of the supporting materials and protect
the specimen structure from outer environments.
In chapter 2, the sample preparation method for structural analysis of
nanomaterials with ET was described. While ET is a powerful method to reconstruct 3D
data of target nanomaterials without averaging the numerous numbers of specimens and
be suitable for capturing the inherent structure, image acquisition processes at various tilt
angles in its procedure often suffer from decreasing the specimen contrast due to the
increase of optical thickness of supporting materials. To tackle the issue, I presented the
application of spherical supporting materials prepared from the molecular assembly of
organofullerenes and succeeded to collect specimen images in constant contrast.
The method is simple that only requires the mixing of nanoparticle dispersions
and organofullerene solutions in THF or DMF to prepare multiple-component
nanospheres, therefore it is applicable for analysis of various specimens from inorganic
nanoparticles to biomolecules including the virus. The key idea is an introduction of a
rate control mechanism of nucleation and growth steps of molecular assembly. In this
research, an equilibrium between neutral fullerene (CnH) and its potassium salt (CnK)
in water was utilized and enable the formation of fullerene assemblies incorporating
specimens from water/buffer. The developed system is expected to put a 360º tomography
of various intended specimens into practice.
57
Chapter 6
K+
R R
Slow addition
of excess H2O
pKa < 13
CnK
(soluble in THF,
DMF and water)
R R
+ KOH
CnH
(Insoluble in aqueous
mixed solvents)
nanoparticles or
biological materials in buffer
Figure 6.1. Preparation of self-assembled core-shell particles by utilizing an equilibrium of
organofullerenes in water and structural analysis of incorporated specimens with ET.
The author anticipates that further chemical derivatization of organofullerenes and
development of the hierarchical molecular assembly systems based on this work would
contribute the structural analyses of wider specimens in EM research. Besides, some
concepts of supra molecular chemistry described in this thesis would be applicable
beyond the organofullerene skeleton, and the present study is expected to become a
milestone of opening the new application field of molecular assembly systems.
58
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